WO2015093759A1 - 탄소지지체와 탄소나노튜브가 직접 연결된 형태의 3차원 구조를 갖는 탄소 나노구조체 제조방법 - Google Patents

탄소지지체와 탄소나노튜브가 직접 연결된 형태의 3차원 구조를 갖는 탄소 나노구조체 제조방법 Download PDF

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WO2015093759A1
WO2015093759A1 PCT/KR2014/011718 KR2014011718W WO2015093759A1 WO 2015093759 A1 WO2015093759 A1 WO 2015093759A1 KR 2014011718 W KR2014011718 W KR 2014011718W WO 2015093759 A1 WO2015093759 A1 WO 2015093759A1
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carbon
metal catalyst
manufacturing
nanostructure
support
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PCT/KR2014/011718
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French (fr)
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박지선
이철승
신권우
김윤진
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전자부품연구원
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Publication of WO2015093759A1 publication Critical patent/WO2015093759A1/ko

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes

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  • the present invention relates to a carbon nanostructure manufacturing method, and more specifically,
  • the present invention relates to a method for producing a carbon nanostructure having a three-dimensional structure in which a carbon support and a carbon nanoleube are directly connected.
  • Carbon materials such as graphene, fullerenes, and carbon nanotubes have excellent properties and can be used in a wide range of solar cells, field emission devices (FEDs), capacitors, and batteries. It is going on.
  • hybrid composites that take advantage of the properties of different types of carbon materials (eg, graphene and carbon nanotubes), including carbon such as graphene, graphite, and carbon fiber.
  • a method of manufacturing a hybrid carbon material in which carbon nanotubes (CNTs) are grown on a material a functional functional group is introduced into the carbon material to form a reaction site, and carbon nanotubes are adsorbed on the reaction site.
  • the direct synthesis method of directly growing carbon nanotubes on the carbon material is more advantageous than the physics / chemical methods described above.
  • Silver may have a variety of methods, but in general, a method of growing carbon nanotubes by coating a metal oxide (a type of buffer) capable of providing nanopores on a surface of a carbon material and supporting a catalyst on the metal oxide is provided.
  • Embodiments of the present invention provide a method for manufacturing a carbon nanostructure having a three-dimensional structure having a form in which carbon nanotubes are directly connected without a separate buffer layer on the carbon support.
  • Task solution
  • a step of supporting a metal catalyst for carbon nanotube synthesis on the surface of a carbon support by using an electroless plating solution; and growing carbon nano-rubber from the metal catalyst, the metal catalyst There may be provided a method of manufacturing carbon nanostructures comprising a two step of growing to be located at the upper tip portion of the virtual base carbon nano-levers.
  • the first step 1-1 step of adsorbing Sn 2+ on the surface of the carbon support;
  • Step 1-2 to form Sn 4 + / Pd on the surface of the carbon support by reacting Sn 2+ with a palladium salt; and electroless plating by immersing the carbon support in a plating bath containing Fe salt and Co salt. It may include steps 1-3 to support the Fe / Co metal catalyst on the surface of the carbon support.
  • the metal catalyst may be positioned at the upper tip portion of the carbon nano-lube.
  • the carbon support may be graphene, graphene oxide, graphene nanoplates, axon, expanded graphite or carbon fiber.
  • an additional carbon nanostructure manufactured by the method for producing a carbon nanostructure according to one aspect of the present invention may be additionally provided.
  • Embodiments of the present invention utilize electroless plating to the surface of a carbon support.
  • the metal catalyst By supporting the metal catalyst and growing the carbon nanotubes from the metal catalyst, the metal catalyst is positioned at the upper tip portion of the carbon nanofluid to directly connect the carbon nano-levers without a separate buffer layer on the carbon support. have.
  • FIG. 1 is a flowchart schematically illustrating a method of manufacturing a carbon nanostructure according to an embodiment of the present invention.
  • FIG. 2 is a conceptual view schematically showing how a carbon nanostructure is manufactured according to the method of manufacturing a carbon nanostructure of FIG. 1.
  • FIG. 3 is an SEM image showing how a metal catalyst is supported on a carbon support according to a test example of the present invention.
  • the metal catalyst is supported on the surface of the carbon support by using electroless plating.
  • the metal catalyst functions as a seed for carbon nanotube synthesis.
  • Carbon supports refer to materials generally composed mainly of carbon.
  • an electroless plating method is used as a method for supporting a metal catalyst on the surface of a carbon support.
  • the electroless plating method is a plating method that is applied to a chemical component of a reducing agent without using electricity, unlike electroplating, and is applied to parts and complex shaped products requiring a uniform plating layer.
  • the electroplating method itself is well known, and specific explanations are omitted.
  • the first step S110 can be divided into the following detailed steps.
  • Step 1-1 corresponds to the sensitization treatment in the process of encapsulating Sn 2+ on the surface of the carbon support.
  • the method of adsorbing Sn 2+ on the surface of the carbon support includes Sn salts. This can be achieved by mixing and reacting with the containing sensitizing solution. have.
  • Kinds of Sn salts include (1) tin chloride, tin oxide, tin fluoride, sodium halide stannate, and butyrate, but not limited thereto.
  • Steps 1-2 correspond to activation during the pretreatment process.
  • the step of forming the Sn 4 VPd on the surface of the carbon support by reacting the adsorbed carbon support with the palladium salt.
  • the method of forming Sn 4 VPd on the surface of the carbon support is mixed with an activation solution containing palladium salt. This can be done by reacting:
  • the activation solution may include water (deionized water), Pd salt and hydrochloric acid.
  • Pd salt water (deionized water), Pd salt and hydrochloric acid.
  • steps 1-3 the Fe / Co metal catalyst is deposited on the surface of the carbon support by electroless plating.
  • the metal catalyst is a growth metal catalyst, which is intended to grow carbon nano-leubes.
  • the specification exemplifies Fe and Co as examples of the transition metal, but in the present invention, the transition metal is added thereto. That is to say, all known metal catalysts available for synthesizing carbon nanoleubes can be used, for example Mo, Ti, V, Cr, Mn, Ni, Cu, Cd, Zn, Ru, Pd, Ag , Pt and Au may be a single metal or an alloy thereof. Meanwhile, the supported amount of the metal catalyst
  • Electroless plating can be achieved by introducing Fe salt, Co salt and reducing agent into the plating bath and immersing the carbon support in the plating bath.
  • the Fe salt may be selected from, but is not limited to, iron chloride, iron sulfate, iron formate, iron acetate, iron citrate, iron oxalate and their hydrates.
  • the Co salt may be selected from the group consisting of cobalt acetate, cobalt carbonate, cobalt chloride, cobalt hydroxide, cobalt nitrate, cobalt sulfate, and their hydrates. It may be a compound capable of reducing precipitation, and is not particularly limited.
  • carbon nanotubes are grown from the metal catalyst supported on the surface of the carbon support, by controlling the contact angle between the carbon support and the metal catalyst, the metal catalyst being formed on the upper tip portion of the carbon nanofluid. Grow to position
  • the carbon nanotubes may be single-walled carbon nano-levers, functionalized single-walled carbon nano-levers, double-walled carbon nanotubes, functionalized double-walled carbon nanotubes, multi-walled carbon nanotubes or functionalized double-walled carbon nanotubes. have.
  • CVD chemical vapor deposition
  • RTCVD High Speed Chemical Vapor Deposition
  • ICP-CVD Inductively Coupled Plasma Chemical Vapor Deposition
  • LPCVD Low Pressure Chemical Vapor Deposition
  • APCVD Atmospheric Chemical Vapor Deposition
  • MOCVD organic chemical vapor deposition
  • PECVD chemical vapor deposition
  • a carbon support supported by the metal catalyst is introduced into a growth reactor, and the reaction gas containing a carbon source (carbon source) is added after increasing the silver content of the reaction vessel to 900 ° C to 1000 ° C. It is possible to grow carbon nanotubes by flowing, in which case, it is possible to control the diameter or length of the carbon nano-rubber by adjusting the pressure of the reaction vessel or the flow rate of the reaction gas. It is possible to use known substances of hydrocarbon origin. Examples of such carbon sources include, but are not limited to, methane, ethane, propane, butane, ethylene, acetylene and benzene.
  • the process of growing carbon nanotubes through chemical vapor deposition can be accomplished using a known process, and specific explanations are omitted.
  • the metal catalyst is positioned at the tip of the carbon nanotube.
  • the growth pattern of the carbon nanotube can be classified into two types, and the metal catalyst is formed at the tip of the carbon nanotube. This is where the metal catalyst is located and the metal catalyst is at the bottom of the carbon nanotubes.
  • the difference between the two types is determined by the contact angle at the growth temperature of the support and the surface of the metal catalyst. The contact angle may vary depending on the type of support and the metal catalyst, the growth temperature, and the like.
  • the metal catalysts were Co and Fe
  • the growth of about 900 o C was found to be over 80 ° in the degree, and the metal catalyst could be located at the tip of the carbon nanotube.
  • the metal catalyst is positioned at the tip of the carbon nano-leave.
  • the metal catalyst is positioned on the upper tip of the carbon nanotube.
  • the carbon support and carbon nanotubes can be directly In the absence of a separate buffer layer, the physical and electrical properties of the carbon nanostructure can be minimized because the thermal and electrical resistance existing between the carbon support and the buffer layer and between the buffer layer and the carbon nanotube can be minimized. This has the advantage that it can be enhanced.
  • the present invention relates to carbon produced by the carbon nanostructure manufacturing method described above.
  • the nano-structure may be additionally provided.
  • the carbon nano-structure is formed by directly connecting carbon nano-levers on a carbon material (carbon support) such as graphene, graphite, and carbon fiber, and includes a solar cell and a field emission device (FED). It can be used in a wide range of applications such as capacitors, batteries, composite fillers, and electrode materials.
  • a carbon material such as graphene, graphite, and carbon fiber
  • FED field emission device
  • the pretreated GNP-Sn 4+ / Pd is a metal catalyst precursor of FeS0 4 2.55g, CoS0 4 0.45g and
  • CNT carbon nanocarbons

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

탄소지지체와 탄소나노튜브가 직접 연결된 형태의 3차원 구조를 갖는 탄소 나노구조체 제조방법이 개시된다. 본 발명의 일 실시예에 따른 탄소 나노구조체 제조방법은 무전해 도금을 이용하여 탄소지지체의 표면에 탄소나노튜브 합성을 위한 금속촉매를 담지하는 1단계; 및 금속촉매로부터 탄소나노튜브를 성장시키되, 금속 촉매가 탄소나노튜브의 상단 팁 부위에 위치하도록 성장시키는 2단계를 포함한다.

Description

명세서
발명의명칭:탄소지지체와탄소나노튜브가직접연결된형태의
3차원구조를갖는탄소나노구조체제조방법 기술분야
[1] 본발명은탄소나노구조체제조방법에관한것으로，보다상세하게는
탄소지지체와탄소나노류브가직접연결된형태의 3차원구조를갖는탄소 나노구조체제조방법에관한것이다.
배경기술
[2] 그래핀,풀러렌,탄소나노튜브와같은탄소소재들은우수한물성을가지고 있으며 ,태양광전지， FED(Field emission device),캐패시터，배터리둥폭넓은 분야에웅용될수있어이들탄소소재들에대한연구가활발하게진행되고 있다.
[3] 특히,최근에는다른형태의탄소소재들 (예컨데，그래핀과탄소나노튜브) 각각의특성을살린하이브리드복합체에대한연구가많이진행되고있다.그 중에서그래핀，흑연,탄소섬유와같은탄소소재상에카본나노류브 (CNT, Carbon Nano Tube)가성장되어있는하이브리드탄소소재를제조하는 방법으로는크게상기탄소소재에기능성작용기를도입하여반웅사이트를 형성하고，상기반응사이트에탄소나노튜브를흡착및치환시켜하이브리드 탄소소재를제조하는물리 /화학적방법과,탄소소재에금속촉매를코팅하고그 표면에탄소나노튜브를성장시키는직접합성법이있다.
[4] 하이브리드탄소소재의경우에는이종소재간의접촉저항을최소화시키는 것이증요한데，이러한측면에서는상술한물리 /화학적방법보다는탄소소재에 탄소나노튜브를직접성장시키는직접합성법이보다유리하다.상기직접 합성법은다양한방식이있을수있으나，일반적으로는탄소소재의표면에 나노기공을제공할수있는금속산화물 (일종의버퍼충)을코팅하고，상기 금속산화물에촉매를담지시켜탄소나노튜브를성장시키는방식이이용되어 왔다.
[5] 그러나，이러한종래방식에서는탄소소재와금속산화물간의계면과,상기 금속산화물과탄소나노튜브간의계면에서발생하는이종소재간의열적, 전기적저항이존재하는바，제조된하이브리드탄소소재는그특성이온전히 구현되지않는문제점이있었다.
발명의상세한설명
기술적과제
[6] 본발명의실시예들은탄소지지체상에별도의버퍼층없이탄소나노튜브가 직접연결된형태를갖는 3차원구조의탄소나노구조체제조방법을제공하고자 한다. 과제해결수단
[7] 본발명의일측면에따르면,무전해도금올이용하여탄소지지체의표면에 탄소나노튜브합성을위한금속촉매를담지하는 1단계;및상기금속촉매로부터 탄소나노류브를성장시키되,상기금속촉매가상기탄소나노류브의상단팁 부위에위치하도록성장시키는 2단계를포함하는탄소나노구조체제조방법이 제공될수있다.
[8] 이때,상기 1단계는,상기탄소지지체표면에 Sn2+를흡착시키는 1-1단계;상기
Sn2+를팔라듐염과반웅시켜상기탄소지지체표면에 Sn4+/Pd를형성시키는 1-2단계;및상기탄소지지체를 Fe염및 Co염을포함하는도금욕에침지시켜 무전해도금함으로써상기탄소지지체표면에 Fe/Co금속촉매를담지시키는 1-3단계를포함할수있다.
[9] 또한,상기 2단계는,상기탄소나노류브의성장시에상기탄소지지체와상기 금속촉매의접촉각올제어함으로써，상기금속촉매가상기탄소나노류브의 상단팁부위에위치하도록할수있다.
[10] 한편,상기탄소지지체는그래핀，산화그래핀，그래핀나노플레이트，혹연,팽창 흑연또는탄소섬유일수있다.
[11] 본발명의다른측면에따르면，본발명의일측면에따른탄소나노구조체 제조방법에의해제조되는탄소나노구조체가추가적으로제공될수있다. 발명의효과
[12] 본발명의실시예들은무전해도금을이용하여탄소지지체의표면에
금속촉매를담지시키고，상기금속촉매로부터탄소나노튜브를성장시킴에있어 상기금속촉매가상기탄소나노류브의상단팁부위에위치하도록함으로써 상기탄소지지체상에별도의버퍼층없이탄소나노류브를직접연결시킬수 있다.
[13] 따라서，버퍼층과의계면에서발생할수있는이종소재간의열적，전기적 저항을최소화시킴으로써보다물리적특성이강화된탄소나노구조체를 제조하는것이가능하다.
도면의간단한설명
[14] 도 1은본발명의일실시예에따른탄소나노구조체제조방법을개략적으로 도시한순서도이다.
[15] 도 2는도 1의탄소나노구조체제조방법에따라탄소나노구조체가제조되는 모습을개략적으로도시한개념도이다.
[16] 도 3은본발명의시험예에따른탄소지지체에금속촉매가담지된모습을 나타내는 SEM이미지이다.
[17] 도 4는본발명의시험예에따른탄소나노구조체의 SEM이미지이다.
[18] 도 5는본발명의시험예에서탄소지지체에담지된금속촉매의양을
변화시킴에따른탄소나노구조체의 SEM이미지이다. 발명의실시를위한최선의형태
[19] 이하,첨부된도면을참조하여본발명의실시예들에대하여구체적으로
설명하도록한다.
[20] 본발명의일실시예에따른탄소나노구조체제조방법은무전해도금을
이용하여탄소지지체의표면에탄소나노튜브합성을위한금속촉매를담지하는 1단계와，상기금속촉매로부터탄소나노튜브를성장시키되，상기금속촉매가 상기탄소나노류브의상단팁부위에위치하도록성장시키는 2단계를포함할수 있다.
[21] 도 1은본발명의일실시예에따른탄소나노구조체제조방법을개략적으로 도시한순서도이고，도 2는도 1의탄소나노구조체제조방법에따라탄소 나노구조체가제조되는모습을개략적으로도시한개념도이다.이하，도 1및도 2를참조하여각단계에대하여구체적으로설명하도록한다.
[22] (1) 1단계 (S110)
[23] 1단계는무전해도금을이용하여탄소지지체의표면에금속촉매를담지하는 단계다.상기금속촉매는탄소나노튜브합성을위한시드 (seed)기능을한다.
[24] 탄소지지체는탄소를주성분으로하는소재일반을의미하는것으로
탄소나노류브는상기탄소지지체의표면에서수직방향으로성장하게된다. 따라서전체적인탄소나노구조체의구조는 3차원구조를갖는다.
[25] 상기탄소지지체의예로는그래핀，산화그래핀，그래핀나노플레이트,흑연, 팽창흑연，탄소섬유둥이있으며이에한정되는것은아니다 (탄소동소체를 포함) ·
[26] 본발명의일실시예에따른탄소나노구조체제조방법에서는탄소지지체의 표면에금속촉매를담지하기위한방법으로무전해도금법을이용하는것을일 특징으로한다.
[27] 무전해도금법은전기도금과는달리전기를사용하지않고환원제의화학적인 화학반웅에의해도금을하는방법으로，균일한도금층을요구하는부품이나 복잡한형상의제품에많이적용되고있는도금법이다.무전해도금법자체는 공지된것인바，구체적인설명은생략하도록한다.
[28] 무전해도금을실시하기위해서상기탄소지지체의표면이전처리될필요가 있다.따라서상기 1단계 (S110)는다음과같은세부단계로구분될수있다.
[29] 1-1다계 (S11D
[30] 무전해도금을실시하기위한전처리공정으로상기탄소지지체의표면은 민감화처리및활성화처리가순차적으로수행되어야한다.
[31] 1-1단계는그증에서민감화처리에해당하는것으로상기탄소지지체표면에 Sn2+를흡착시키는단계다.상기탄소지지체표면에 Sn2+를흡착시키는방법은 상기탄소지지체를 Sn염을포함하는민감화용액에혼합하여반웅시킴으로써 이루어질수있다.상기민감화용액은물 (탈이은수)， Sn염및염산을포함할수 있다. Sn염의종류로는염화 (제 1)주석，산화주석,불화주석,할로겐화나트륨 주석산염및아주석산염등이있으며，이에한정되는것은아니다.탄소지지체 표면에 Sn2+를흡착시킨후에는탄소지지체와반웅하지않은여분의 Sn2+를 제거하기위해복수회에걸쳐세척 (수세)이수행될수있다 (이상 sin).
[32] 1-2단계 (S112)
[33] 1-2단계는전처리공정중활성화처리에해당하는것으로 Sn2+가표면에
흡착된탄소지지체를팔라듐염과반웅시켜상기탄소지지체표면에 Sn4VPd를 형성시키는단계다.상기탄소지지체표면에 Sn4VPd를형성시키는방법은상기 탄소지지체를팔라듐염올포함하는활성화용액에흔합하여반웅시킴으로써 이루어질수있다.반웅식은다음과같다.
[34] Sn2+ + Pd2+→ Pd°Sn +
[35] 상기활성화용액은물 (탈이온수)， Pd염및염산을포함할수있다. Pd염의
종류로는염화괄라듐,괄라듐염화나트륨,팔라듐염화칼륨,팔라듐염화암모늄， 황산팔라듐，질산팔라듐，팔라듐아세테이트및산화팔라듬등이있으며，이에 한정되는것은아니다.상기반웅을통해탄소지지체표면에 Sn4+/Pd를형성시킨 후에는반웅하지않은여분의 Pd2+를제거하기위해복수회에걸쳐세척 (수세)이 수행될수있다 (이상 S112).
[36] 1-3다계 (ᅳ S113)
[37] 1-3단계는무전해도금을통해탄소지지체표면에 Fe/Co금속촉매를
담지시키는단계다.상기금속촉매는탄소나노류브를성장시키기위한것으로, 전이금속촉매에해당한다.본명세서에서는상기전이금속의예로 Fe및 Co를 예시하고있으나，본발명에서상기전이금속은이에한정되지않는다.즉, 탄소나노류브를합성하기위해이용가능한공지의금속촉매는모두사용될수 있으며，예로는 Mo, Ti, V, Cr, Mn, Ni, Cu, Cd, Zn, Ru, Pd, Ag, Pt및 Au둥의단일 금속또는이들의합금일수있다.한편,상기금속촉매의담지량을
조절함으로써，이후 2단계에서성장될탄소나노류브의합성밀도를제어하는 것이가능하다.
[38] 무전해도금은도금욕에 Fe염, Co염및환원제등을투입하고，상기도금욕에 탄소지지체를침지함으로써이루어질수있다.
[39] Fe염은염화철，황산철，포름산철,아세트산철,시트르산철，옥살산철및이들의 수화물로이루어지는군으로부터선택될수있으며，이에한정되지않는다. Co염은아세트산코발트,탄산코발트,염화코발트，수산화코발트，질산코발트, 황산코발트및이들의수화물로이루어지는군으로부터선택될수있으며，이에 한정되지않는다.환원제는상기 Fe염및 Co염으로부터 Fe및 Co를환원석출할 수있는화합물이면되고특별히한정되지는않는다.
[40] 상기무전해도금을통해탄소지지체표면에 Fe/Co금속촉매를담지시킨
후에는반웅하지않은여분의 Fe2+, Co2+및기타불순물들을제거하기위해 복수회에걸쳐세척 (수세)이수행될수있다 (이상 S113). [41] (2) 2단계(3120)
[42] 2단계는탄소지지체표면에담지된상기금속촉매로부터탄소나노튜브를 성장시키는단계다.이때,탄소지지체와금속촉매의접촉각을제어함으로써， 상기금속촉매가탄소나노류브의상단팁부위에위치하도록성장시킨다.
[43] 상기탄소나노튜브는단일벽탄소나노류브,기능화된단일벽탄소나노류브， 이증벽탄소나노튜브，기능화된이증벽탄소나노튜브，다중벽탄소나노튜브 또는기능화된다중벽탄소나노튜브일수있다.
[44] 탄소나노튜브를성장시키는방법으로는화학기상증착법 (CVD, chemical vapor deposition)이이용될수있다.여기에서상기화학기상증착법은
고속화학기상증착 (RTCVD),유도결합플라즈마화학기상증착 (ICP-CVD),저압 화학기상증착 (LPCVD),상압화학기상증착 (APCVD),금속
유기화학기상증착 (MOCVD),화학기상증착 (PECVD)등을포함하는개념임을 밝혀둔다.
[45] 예를들어,상기금속촉매가담지된탄소지지체를성장반응기에도입하고 상기반웅기의은도를 900°C내지 1000°C로증가시킨후에탄소소스 (탄소 공급원)를포함하는반웅기체를유동시킴으로써탄소나노튜브를성장시킬수 있다.이때,상기반웅기의압력이나상기반웅기체의유량을조절함으로써 탄소나노류브의직경이나길이를제어하는것이가능하다.이때，상기탄소 소스는지방성탄화수소，방향족탄화수소둥의공지된물질을이용하는것이 가능하다.이러한탄소소스의예로는메탄,에탄，프로판，부탄，에틸렌， 아세틸렌，벤젠등이있으며，이에한정되지는않는다.이와같이
화학기상증착법을통하여탄소나노튜브를성장시키는공정은공지의공정을 이용하여이루어질수있는바，구체적인설명은생략하도록한다.
[46] 한편，탄소나노튜브의성장시에탄소지지체와상기금속촉매의접촉각을
제어함으로써，상기금속촉매가상기탄소나노튜브의상단팁 (tip)부위에 위치되도록한다.탄소나노튜브의성장형태는크게두가지로구분될수 있으며,금속촉매가탄소나노튜브의상단팁 (tip)에위치하는형태와금속촉매가 탄소나노튜브의하단 (bottom)에위치하는형태가그것이다.두형태의차이는 성장온도에서의지지체및금속촉매의표면상호작용에따른접촉각 (contact angle)에의해결정되는데，상기접촉각은지지체와금속촉매의종류,성장온도 등에의해달라질수있다.본발명의발명자들은탄소지지체를
그래핀나노플레이트로하고，금속촉매를 Co및 Fe로하였을때에 900oC정도의 성장은도에서접촉각이 80°이상이되는바，금속촉매가탄소나노튜브의팁 부위에위치될수있음을발견하였으며,상술한조건설정올통해상기 금속촉매가상기탄소나노류브의상단팁 (tip)부위에위치되도록
탄소나노류브를성장시키는것이가능하다.
[47] 상기와같이금속촉매가탄소나노튜브의상단팁부위에위치되도록
성장시키는경우에는탄소지지체와탄소나노튜브가별도의버퍼층없이직접 연결된형태를가지게된다.이와같이별도의버퍼층이존재하지않는경우에는 탄소지지체와버퍼층,그리고버퍼층과탄소나노튜브간에존재하던열적， 전기적저항이최소화될수있으므로탄소나노구조체의전기，열특성둥의 물리적특성이강화될수있다는장점이있다.
[48] 본발명은상술한탄소나노구조체제조방법에의해제조되는탄소
나노구조체를추가적으로제공할수있다.상기탄소나노구조체는그래핀， 흑연,탄소섬유와같은탄소소재 (탄소지지체)상에카본나노류브가직접 연결되어성장된것으로，태양광전지， FED(Field emission device),캐패시터， 배터리，복합소재용필러,전극소재등과같은폭넓은분야에서사용가능하다. 또한，상기탄소나노구조체는비표면적이매우넓으므로다른복합소재에 소량을첨가하여도높은물성향상효과를나타낼수있다는장점이있다.
[49] 이하에서는본발명의구체적인시험예에대하여설명하도록한다.다만，
하기의시험예가본발명을한정하지않음은자명하다.
[50] 시험예
[51] (1)전처리공정
[52] Deionized (DI) water 500niL에 HC14mL, SnCl2 3g，및그래핀나노플레이트 (이하, GNP) lg을초음파분쇄기를이용하여 60분간균질흔합하고, GNP와반응하지 않은여분의 Sn2+를제거하기위해 20 mesh size를갖는 sieve (체)를사용하여 위의흔합액을깨끗한물과함께통과시킴으로써여러번세척하였다.세척된 GNP-Sn2+는다시 Deionized (DI) water 500mL, HC1 1.25mL,그리고 PdCl20.05g과 함께초음파분쇄기를통해 60분간균질흔합되었고， GNP-Sn2+와반웅하지않은 여분의 Pd2+을제거하기위해위와같이 20/ m mesh size를갖는 sieve (체)를 사용하여흔합액을깨끗한물과함께통과시킴으로써여러번세척한후
60°C에서하루동안건조시켰다.
[53] (2)무전해도금공정
[54] 전처리된 GNP-Sn4+/Pd는금속촉매전구체인 FeS04 2.55g, CoS04 0.45g및
환원제인 NaH2P02 H20 2g, C6H507Na3 6g, H3B03 3g, NaOH 2g및 Deionized (DI) water 500mL와함께 90°C에서 30분간교반하여균질흔합됨으로써무전해 도금이수행되었다.다음으로, GNP-Sn4+/Pd와반웅하지않은여분의 Fe2+, Co2+및 기타불순물들은 20 m mesh size를갖는 sieve (체)를사용하여흔합액을깨끗한 물과함께통과시킴으로써여러번세척하여제거되었다.세척공정을마친 GNP-Fe/Co촉매담지체는 60oC에서하루동안건조시켰다.관련하여，도 3은본 발명의시험예에따른그래핀나노플레이트에 Fe/Co금속촉매가담지된모습을 나타내는 SEM이미지이다 (KANC 5.0Kv, 6.0mmx7.00k SE(U)).
[55] (3)탄소나노튜브의성장
[56] GNP상에탄소나노류브 (이하, CNT)합성용금속촉매가담지된 GNP-Fe/Co 촉매담지체는열화학기상증착법을통해석영류브안에서반웅시켰고， 구체적으로는 900°C, Ar(500 sccm)분위기하에서 40분간어닐링후, CH4(500 sccm)분위기에서 60분간 CNT를합성하여 GNP상에 CNT가성장된 3차원탄소 나노구조체를제작하였다.이때， 900°C합성온도에서 GNP와금속촉매간의 표면상호작용에의한접촉각이 80°이상발생하는바, CNT합성메커니즘에 의하여최종적으로금속촉매가 CNT의상단팁에위치하는모폴로지가 형성되었다.관련하여，도 4는본발명의시험예에따른탄소나노구조체의 SEM 이미지이다 (S4800 15.0Kv, 8.2mmx2.00k SE(U)).
[57] 한편， GNP에담지되는금속촉매의양을달리하여상기시험을반복하여
다양한합성밀도를갖는 CNT를 GNP상에성장시켰으며,이에대해서는도 5에 SEM이미지로나타내었다.
[58] 이상，본발명의실시예들에대하여설명하였으나，해당기술분야에서통상의 지식을가진자라면특허청구범위에기재된본발명의사상으로부터벗어나지 않는범위내에서，구성요소의부가，변경，삭제또는추가등에의해본발명을 다양하게수정및변경시킬수있을것이며,이또한본발명의권리범위내에 포함된다고할것이다.

Claims

청구범위
[청구항 1] 무전해도금을이용하여탄소지지체의표면에탄소나노튜브
합성을위한금속촉매를담지하는 1단계;및 상기금속촉매로부터탄소나노튜브를성장시키되,상기 금속촉매가상기탄소나노류브의상단팁부위에위치하도록 성장시키는 2단계를포함하는탄소나노구조체제조방법.
[청구항 2] 청구항 1에있어서，
상기 1단계는，
상기탄소지지체표면에 Sn2+를흡착시키는 1-1단계;
상기 Sn2+를팔라듐염과반웅시켜상기탄소지지체표면에 Sn4+
/Pd를형성시키는 1-2단계;및
상기탄소지지체를 Fe염및 Co염을포함하는도금욕에침지시켜 무전해도금함으로써상기탄소지지체표면에 Fe/Co금속촉매를 담지시키는 1-3단계를포함하는탄소나노구조체제조방법.
[청구항 3] 청구항 2에있어서,
상기 2단계는,
상기탄소나노튜브의성장시에상기탄소지지체와상기 금속촉매의접촉각을제어함으로써，상기금속촉매가상기 탄소나노튜브의상단팁부위에위치하도록하는탄소나노구조체 제조방법.
[청구항 4] 청구항 1내지청구항 3중어느한항에있어서，
상기탄소지지체는그래핀,산화그래핀，그래핀나노플레이트， 혹연，팽창혹연또는탄소섬유인탄소나노구조체제조방법 .
[청구항 5] 청구항 1내지청구항 3증어느한항에따른탄소나노구조체 제조방법에의해제조되는탄소나노구조체.
PCT/KR2014/011718 2013-12-17 2014-12-02 탄소지지체와 탄소나노튜브가 직접 연결된 형태의 3차원 구조를 갖는 탄소 나노구조체 제조방법 WO2015093759A1 (ko)

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KR102185266B1 (ko) * 2018-09-19 2020-12-01 한국전자기술연구원 탄소 소재 제조용 수세 장치
KR102081661B1 (ko) 2019-06-24 2020-02-27 대주전자재료 주식회사 그래핀-탄소나노튜브 복합체 및 이의 제조 방법
KR20210128176A (ko) 2020-04-16 2021-10-26 주식회사 그래핀올 그래핀-탄소나노튜브 복합체의 제조방법
KR20220085691A (ko) 2020-12-14 2022-06-22 한국전자기술연구원 무전해도금 장치 및 이를 이용한 다차원 탄소나노구조체 제조방법

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